CN117721452A - Titanium zirconium passivation stabilization method for aluminum surface treatment line for vehicle body - Google Patents
Titanium zirconium passivation stabilization method for aluminum surface treatment line for vehicle body Download PDFInfo
- Publication number
- CN117721452A CN117721452A CN202311751629.5A CN202311751629A CN117721452A CN 117721452 A CN117721452 A CN 117721452A CN 202311751629 A CN202311751629 A CN 202311751629A CN 117721452 A CN117721452 A CN 117721452A
- Authority
- CN
- China
- Prior art keywords
- passivation
- titanium
- zirconium
- vehicle body
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002161 passivation Methods 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 28
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004381 surface treatment Methods 0.000 title claims abstract description 14
- 230000006641 stabilisation Effects 0.000 title abstract description 3
- 238000011105 stabilization Methods 0.000 title abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- -1 titanium ions Chemical class 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 206010049040 Weight fluctuation Diseases 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000013024 troubleshooting Methods 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Abstract
The invention provides a titanium zirconium passivation stabilization method of an aluminum surface treatment line for a vehicle body, which aims to ensure the corrosion resistance and durability of the aluminum for the vehicle body, the surface of a vehicle plate product is usually provided with a titanium zirconium passivation film weight requirement, the content of zirconium and titanium in a surface oxide film is converted into metallic zirconium and metallic titanium, and the content of the zirconium and the titanium needs to be ensured to be 1-12mg/m 2 Within the range. If the content is low, the thickness of the surface oxide film is insufficient, and the corrosion resistance and durability cannot meet the requirements of the vehicle body plate strip. If the content is too high, the surface oxide film becomes brittle and is liable to crack. The corrosion resistance and durability required for the vehicle body panel are not obtained, and the manufacturing cost is increased due to the large amount of materials. The invention redetermines parameters such as pH, temperature, conductivity, passivation time and the like suitable for industrial rapid stable production by tracking the production process of the production line, and can ensure the titanium zirconium in the mass production processThe films are overlapped and stable.
Description
Technical Field
The invention belongs to the field of aluminum passivation treatment, and particularly relates to a titanium zirconium passivation stabilizing method for an aluminum surface treatment line for a vehicle body.
Background
The aluminum alloy is easy to generate oxidation reaction, a layer of compact aluminum oxide film is often formed on the surface of the aluminum plate, and the film weight difference of different positions of the aluminum plate is large, so that the production stability of the downstream process is obviously affected. In order to solve the problem, the surface treatment is required to be carried out on the aluminum alloy, and the chromate chemical conversion coating is the most commonly used surface anti-corrosion treatment mode for the aluminum alloy, but chromium is extremely toxic, cancerogenic and serious in environmental pollution, and is gradually forbidden by the industry. The popularization of the green nontoxic environment-friendly aluminum alloy surface treatment process is significant.
The titanium zirconium passivation process is green and nontoxic and is firstly used in aluminum tank industries such as aluminum tanks, and then research and development are carried out in the field of titanium zirconium passivation by international company research and development parts such as Parker, kami Ten Germany, and various titanium zirconium passivation products are developed for industrial production, and the titanium zirconium passivation process gradually replaces a chromate passivation process in part of industries through industrial application for many years.
The conventional titanium zirconium passivation solution generally contains H 2 TiF 6 、H 2 ZrF 6 The formation of the titanium-zirconium passivation film can effectively enhance the binding force between the organic coating and the substrate while the formation of the passivation film can prevent corrosion occurring under the paint film. The research result shows that the passivation film consists of an alumina layer close to the metal surface and a compound layer close to the surface, wherein the compound layer contains Zr, O and F, the content of Ti and Zr in the passivation film is very low, three elements are uniformly distributed on the surface, and the Ti and Zr elements are generally only present on the surface of a substrate and around active points at the interface.
In order to ensure the corrosion resistance and durability of the aluminum for the vehicle body, the surface of the vehicle plate product is generally provided with a titanium zirconium passivation film. If the thickness of the surface passivation film is insufficient, the corrosion resistance and durability cannot meet the requirements of the vehicle body panel strip. If the thickness of the surface passivation film is too high, the surface oxide film becomes brittle and is liable to crack. The corrosion resistance and durability required by the vehicle body plate are not met, and the manufacturing cost is increased due to the fact that a large amount of materials are used.
The industrial production of the aluminum surface passivation treatment for the vehicle body is usually completed on a continuous surface treatment line, the passivation process is required to be quickly and stably realized in order to improve the efficiency and reduce the cost, the passivation film weight control difficulty is high due to the quick passivation, the problems of unqualified passivation film weight and large film weight fluctuation exist in the mass production process, the product delivery is easily affected by batch defective products, the troubleshooting difficulty is high after the defective products are produced, and the reason of the fluctuation of titanium and zirconium cannot be always determined. How to ensure the qualification and stability of the titanium zirconium is the key of the mass production of the vehicle body plate products.
Disclosure of Invention
The invention aims to provide a titanium zirconium passivation stabilizing method for an aluminum surface treatment line for a vehicle body, which realizes rapid and stable passivation in industrial production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the titanium zirconium passivation solution mainly comprises fluorozirconic acid, fluorotitanic acid and ammonium bifluoride, wherein the concentration of titanium ions is 50-200mg/l, the concentration of zirconium ions is 100-400mg/l, and the concentration of aluminum ions is less than or equal to 100mg/l.
Further, in the passivation solution, the pH control range is 3.5-4.5, the pH is the optimal range for titanium zirconium film formation, and too low pH can promote the dissolution of the passivation film, so that the passivation film thickness is insufficient; too high pH can lead to rough passivation film structure, uneven passivation film and damage corrosion resistance of the passivation film. In order to ensure the pH value control range, the bath solution needs to be taken off-line to detect the pH value every 8 hours in the production process, and the pH value of the bath solution is timely adjusted and calibrated on-line pH detector when abnormality is found.
Further, in the passivation solution, the temperature control range is 45-55 ℃.
Further, in the passivation solution, the conductivity control range is 1500-2500us/cm, in order to ensure the conductivity control range, the conductivity is required to be detected offline by taking the bath solution every day, and when abnormality is found, the conductivity of the bath solution is timely adjusted and calibrated to an online conductivity detector.
Furthermore, in the passivation solution, the concentration of titanium ions is controlled to be 50-200mg/l, the activity of the titanium ions is high in the passivation process, and the target film weight can be realized by low required concentration.
Furthermore, in the passivation solution, the concentration of zirconium ions is 100-400mg/l, the activity of zirconium ions is low in the passivation process, and the target film weight can be realized only by higher concentration.
Furthermore, in the passivation solution, the concentration of aluminum ions is controlled within 100mg/l, the aluminum ions belong to impurity atoms, and the passivation effect is influenced by the excessive high aluminum ions, so that the weight fluctuation of the passivation film is large.
Further, in the passivation method, passivation is performed by adopting a spraying mode, and passivation can be completed within 6-10 s.
The continuous surface treatment line titanium zirconium passivation mode provided by the invention is to spray by using the spray boom, when the speed of the strip passing through the passivation tank is constant, the passivation reaction time is adjusted by controlling the opening row number of the spray boom in the passivation tank, and as the opening row number of the spray boom is discontinuous, when the opening row number is fixed, the actual reaction time difference of the strip can be caused by different running speeds of the strip. Under certain specific speed settings, the actual passivation time of the strip material is greatly different from the set time, when the time difference exceeds 0.5s, the speed is adjusted so that the time difference delta T is controlled within 0.5s, and the actual reaction time is calculated according to the following formula:
T 1 =D×(N-1)/V
ΔT=T 1 -T 2
T 1 for the actual passivation time T 2 For the passivation time set point (T 2 =6-10 s), Δt is the difference between the actual passivation time and the set passivation time, D is the distance between the boom beams, N is the boom beam opening row number, and V is the process segment speed.
Further, in the passivation method, the machine train speed of the production line is 20-40m/min.
Further, in the passivation method, the overflow amount is controlled to be 200-400L/h, the upper limit is set when the aluminum ion exceeds 100mg/L, and the lower limit is set when the aluminum ion concentration is lower than 100mg/L.
Further, in the passivation method, the passivation liquid pressure is controlled to be 2.0-2.3bar, and the flow is controlled to be 30-150m 3 /h。
The innovation of the invention is mainly as follows:
(1) The passivation reaction is finished in a spraying mode on the surface treatment line, and passivation can be finished within 10 seconds, and parameters such as pH, temperature, conductivity, passivation time and the like suitable for production in a spraying mode of the production line are redetermined by tracking the production process of the production line, so that compared with the passivation time of 2 minutes in the CN101161861 embodiment, the passivation can be quickly and stably realized by the method;
(2) The invention points out the relation between the process section speed and the actual passivation time, and provides a method for determining the reasonable process section speed. In addition, the invention provides the influence of the concentration of aluminum ions in the passivation solution on the passivation effect, and determines the given value of the overflow amount according to the concentration of aluminum ions.
Detailed Description
The invention provides a method for stabilizing titanium-zirconium passivation of an aluminum surface treatment line for a vehicle body, wherein the film forming process of a titanium-zirconium conversion film on the surface of an aluminum alloy is driven by electrochemistry, the process can be roughly divided into three stages of acid activation of an aluminum alloy matrix, rapid growth of the conversion film and deceleration growth of the conversion film, the cathode is an intermetallic compound such as Al (Fe, mn) Si, and the like, and hydroxides or oxides of titanium, zirconium and aluminum are preferentially deposited on the surface of the intermetallic compound such as Al (Fe, mn) Si, and then gradually diffused on the surface of the whole aluminum alloy matrix.
Research shows that the corrosion resistance of the titanium conversion film on the surface of the aluminum alloy is inferior to that of the zirconium conversion film under the condition that two elements of zirconium and titanium exist independently. When two elements of zirconium and titanium exist in the conversion solution at the same time, the titanium and the zirconium exist on the surface of the aluminum alloy in the form of complex compounds of Zr-Ti-F-O-Al, and the corrosion resistance of the film is superior to that of H 2 TiF 6 Or H 2 ZrF 6 And (5) independently forming a film.
In particular, when the pH value of the passivation solution is controlled to be 3.5-4.5 and the pH value is too low, the Ti-Zr conversion film is partially dissolved in the stronger acid solution to influence Ti in the passivation solution 4+ And Zr (Zr) 4+ The titanium-zirconium conversion film is deposited on the surface of the aluminum alloy, so that the film forming speed is reduced, and the corrosion-resistant conversion film cannot be formed rapidly. With increasing pH, ti in solution 4+ And Zr (Zr) 4+ The aluminum alloy can be deposited on the surface of the aluminum alloy more easily, and a layer of conversion film with good corrosion resistance can be formed on the surface of the aluminum alloy. When the pH is more than 4.5, the conversion liquid is not stable any more, a compact and uniform conversion film cannot be formed on the surface of the aluminum alloy, and the corrosion resistance of the conversion film is reduced.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
A method for passivating and stabilizing aluminum surface treatment line titanium zirconium for a vehicle body comprises the following steps:
1) The passivation solution contains fluorozirconic acid, fluorotitanic acid and ammonium bifluoride, the ion concentration of the passivation solution needs to be detected periodically, the concentration of titanium ions needs to be ensured to be 50-200mg/l, the concentration of zirconium ions is 100-400mg/l, and the concentration of aluminum ions is less than or equal to 100mg/l;
2) The conductivity of the passivation tank liquid can be adjusted by automatically adding fluorozirconic acid and fluorotitanic acid, and the conductivity needs to be controlled at 1500-2500us/cm;
3) Adjusting the pH of the passivation tank liquid by automatically adding ammonium bifluoride, wherein the pH is required to be controlled to be 3.5-4.5;
4) Setting the temperature of the passivation tank liquor to be 45-55 ℃, wherein the temperature is the optimal temperature range, and the passivation film is thinner due to the insufficient activity of the passivation liquor below the optimal temperature, and the non-uniformity degree of the passivation film is increased above the optimal temperature;
5) Setting the reaction time of the passivation tank to be 6-12s; the passivation solution pressure is 2.0-2.3bar, and the flow is 30-150m 3 /h; the overflow amount is 200-400L/h;
6) And setting the speed of the machine array to be 20-40m/min, finishing inlet uncoiling and outlet coiling, taking a blank sample at the inlet, and taking a passivation sample at the outlet for detecting the weight of the passivation film.
The bath solution concentrations of the examples are shown in the following table:
the process parameters and passivation film weights of the examples are shown in the following table
The results show that the passivation solutions of examples 1-7 all meet the requirements of the invention in terms of titanium, zirconium and aluminum ion concentration, and the flow rate, pressure and overflow amount also meet the requirements of the invention, and from example 5, when the production line speed is increased to 32m/min, the continuous surface treatment line passivation section is opened by one more row of spray bars to meet the set 8s passivation time, and the flow rate is increased to 75 m under the condition of unchanged pressure 3 And/h. The passivation solution temperature, pH, conductivity and passivation time in examples 1-5 are all set according to the requirements of the invention, and the detection result of the titanium zirconium on the surface of the product meets the requirements of the automobile plate host factory of 1-12mg/m 2 And the titanium-zirconium film is overlapped and kept stable in the actual mass production process. The process stage speed was 32m/min in example 5, and the passivation film weight was thicker in example 5 compared to examples 1-4 for the same 8s passivation time, because the actual passivation time at 32m/min was longer. The process stage velocity in example 6 was the same as in example 5 but the pH was 3.31 lower than 3.53 in example 5, and the results showed that the titanium zirconium film weight in example 6 was less. Both the pH and the passivation conductivity in example 7 are outside the claimed range of the present invention, and the results indicate that the titanium zirconium film weight in example 7 is at a lower limit or even unacceptable.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. A method for stabilizing the passivation of titanium zirconium of an aluminum surface treatment line for a vehicle body is characterized by comprising the following steps: the rapid passivation is realized by using a spraying mode, the pH value of the passivation solution is 3.5-4.5, the passivation temperature is 45-55 ℃, and the conductivity is 1500-2500us/cm.
2. The method of claim 1, wherein: the set passivation time is 6-10s, the actual passivation time and the set passivation time are not different by more than 0.5s, otherwise, the production line speed is required to be adjusted to control the actual passivation time and the set passivation time within 0.5 s.
3. The method of claim 2, wherein: the line speed of the production line is 20-40m/min.
4. The method of claim 1, wherein: the passivation solution pressure is 2.0-2.3bar, and the flow is 30-150m 3 /h。
5. The method of claim 1, wherein: the overflow amount is 200-400L/h.
6. The method of claim 1, wherein: the passivation solution mainly comprises fluorozirconic acid, fluorotitanic acid and ammonium bifluoride, wherein the concentration of titanium ions is 50-200mg/l, the concentration of zirconium ions is 100-400mg/l, and the concentration of aluminum ions is less than or equal to 100mg/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311751629.5A CN117721452A (en) | 2023-12-19 | 2023-12-19 | Titanium zirconium passivation stabilization method for aluminum surface treatment line for vehicle body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311751629.5A CN117721452A (en) | 2023-12-19 | 2023-12-19 | Titanium zirconium passivation stabilization method for aluminum surface treatment line for vehicle body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117721452A true CN117721452A (en) | 2024-03-19 |
Family
ID=90201219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311751629.5A Pending CN117721452A (en) | 2023-12-19 | 2023-12-19 | Titanium zirconium passivation stabilization method for aluminum surface treatment line for vehicle body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117721452A (en) |
-
2023
- 2023-12-19 CN CN202311751629.5A patent/CN117721452A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3239347B1 (en) | Zinc alloy plated steel material having excellent weldability and processed-part corrosion resistance and method of manufacturing same | |
| US9550208B2 (en) | Method for selectively phosphating a composite metal construction | |
| EP2366811B1 (en) | Composition for chemical conversion treatment, and process for production of members provided with anticorrosive coatings | |
| US20090139872A1 (en) | Method for producing a sheet steel product protected against corrosion | |
| CN101045980A (en) | High aluminium zinc alloy hot dip coating process for iron steel product | |
| CN111962001A (en) | Production and surface quality control method of cold-rolled thick-zinc-layer hot-dip pure-zinc steel strip | |
| KR101879093B1 (en) | Alloy plated steel having excellent corrosion resistance and surface quality, and method for manufacturing the same | |
| EP0815295A1 (en) | Reducing or avoiding surface irregularities in electrophoretic painting of phosphated metal surfaces | |
| CN117721452A (en) | Titanium zirconium passivation stabilization method for aluminum surface treatment line for vehicle body | |
| CN1034681C (en) | Method for making manganese-containing zinc phosphate layer on surface of zinc-plated steel | |
| CN113430478A (en) | Method for eliminating zinc corrugation defect of alloyed hot-dip galvanized steel sheet | |
| KR101657843B1 (en) | Zn ALLOY PLATED STEEL SHEET HAVING EXCELLENT WELDABILITY AND PROCESSED PART CORROSION RESISTANCE AND METHOD FOR MANUFACTURING THE SAME | |
| JP2968147B2 (en) | Acid displacement plating solution composition for zinc-containing metal plated steel sheet | |
| US20230145863A1 (en) | Method for producing hardened steel components with a conditioned zinc anti-corrosive layer | |
| KR102538202B1 (en) | Two-step pretreatment of aluminum, particularly aluminum casting alloys, including pickling and conversion treatment | |
| US10458022B2 (en) | Optimized process control in the anti-corrosive metal pretreatment based on fluoride-containing baths | |
| US20200308711A1 (en) | Method for the anti-corrosion and cleaning pretreatment of metal components | |
| EP0584364B1 (en) | Al-Si-Cr-PLATED STEEL SHEET EXCELLENT IN CORROSION RESISTANCE AND PRODUCTION THEREOF | |
| JP3114610B2 (en) | Method for producing alloyed hot-dip galvanized steel sheet having Fe-Ni-O-based coating | |
| KR100343010B1 (en) | The method of high image clarity alloyed hot dip galvanized steel for outcase of automobile | |
| CN115279944B (en) | Method for producing a hardened steel component having a zinc alloy corrosion protection layer | |
| KR950012815B1 (en) | Method for manufacturing a golvanized steel sheet to treated chromate | |
| JPH05148660A (en) | Treatment of surface of aluminum alloy | |
| CN114107865A (en) | Preparation method of zinc-aluminum-magnesium alloy coating steel | |
| JP2576724B2 (en) | Chromate treatment method for galvanized steel sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |